SE1750567A1 - Methods for recovering cesium or rubidium values from ore orother materials - Google Patents

Abstract

A method to liberate and recover cesium, rubidium, or both from ore or other material is described. The method involves heating the ore or other material in the presence of at least one reactant. The heating is such that it liberates at least a portion of the cesium or rubidium or both from the ore. Cesium or rubidium or both resulting from the method are further described.

Description

METHODS FOR RECOVERING CESIUM OR RUBIDIUM VALUESFROM ORE OR OTHER MATERIALS BACKGROUND OF THE INVENTION id="p-1"

[0001] This application claims the benefit under 35 U.S.C. §ll9(e) of prior U.S. ProvisionalPatent Application No. 62/078,43l, f1led November l2, 2014, which is incorporated in its entiretyby reference herein. id="p-2"

[0002] The present invention relates to liberating and/or recovering at least one metallicelement from ore. More particularly, the present invention relates to methods for recoveringcesium, rubidium, or both from ore or other material. id="p-3"

[0003] Cesium salts, such as cesium forrnate, are increasingly being discovered as usefulcomponents or additives for a variety of industrial applications, such as in the hydrocarbonrecovery areas. However, deposits of "primary" ore, that is, ore that contains high amounts ofcesium with insignificant amounts of undesirable impurities, are rare, and operators have longsought techniques to enhance recovery of cesium and/or rubidium from known deposits of ore,such as primary ore and secondary ore, or other materials containing cesium and/or rubidium. Itwould be highly desirable to develop methods that work well no matter what the cesium and/orrubidium content is in the ore. In other words, it would be usefial to have methods that work wellwith primary ore and/ or secondary ore, or other materials containing cesium and/ or rubidium.[0004] However, cesium-containing secondary ore, while available, presents major problemswith regard to recovering the cesium from such ore. For instance, the expense of recoveringsignificant amounts of cesium from low yield ore can be quite time consuming and expensivebased on known methods. These same problems also can exist with rubidium containing ore or ore containing cesium and rubidium. id="p-5"

[0005] Accordingly, there is a need in the industry to develop methods for recovering thehighly sought and valued minerals bearing cesium, rubidium, or both, from ore, such as primary and/or secondary ore (also referred to as cesium-containing secondary ore) or other materials.

SUMMARY OF THE PRESENT INVENTION id="p-6"

[0006] A feature of the present invention is to provide a method to effectively recover cesium,rubidium, or both, from all types of cesium bearing ore and/or rubidium ore, Whether high yieldbearing ore or low yielding bearing ore. id="p-7"

[0007] A fiarther feature of the present invention is to provide methods to utilize the cesium,rubidium, or both, recovered from ore in the production of cesium-containing fluids, such ascesium forrnate and the like. id="p-8"

[0008] Additional features and advantages of the present invention Will be set forth in part inthe description that follows, and in part Will be apparent from the description, or may be leamedby practice of the present invention. The features and other advantages of the present inventionWill be realized and attained by means of the elements and combinations particularly pointed outin the description and appended claims. id="p-9"

[0009] To achieve these and other advantages, and in accordance With the purposes of thepresent invention, as embodied and broadly described herein, the present invention relates tomethods to recover cesium, rubidium, or both from ore and/or other materials containing cesiumand/or rubidium. The method involves heating ore or other material containing at least cesium,rubidium, or both With at least one reactant. The reactant is an oxide of a metal, or a carbonateof a metal, or a hydroxide of a metal, or a hydrate of a metal, that is capable of displacing cesium oxide, rubidium oxide, or both from the ore or other material. The heating is at a temperature sufficient to liberate at least a portion of the cesium, rubidium, or both from the oreor other material. For instance, this temperature can be l,000° C or higher. Examples of thereactant include, but are not limited to, lime, hydrated lime, lime in solution, or calciumcarbonate, or any combinations thereof id="p-10"

[0010] The present inVention further relates to cesium oxide or rubidium oxide or bothobtained from any of the methods of the present inVention. id="p-11"

[0011] It is to be understood that both the foregoing general description and the followingdetailed description are exemplary and explanatory only and are intended to proVide a fiJrtherexplanation of the present inVention, as claimed. id="p-12"

[0012] The accompanying draWings, Which are incorporated in and constitute a part of thisapplication, illustrate some of the features of the present inVention and together With thedescription, serVe to explain the principles of the present inVention. The descriptions are not intended to limit the scope or the spirit of the inVention.

BRIEF DESCRIPTION OF DRAWINGS[0013] Fig. l is a floW diagram shoWing one process of the present inVention for recoVeringcesium, rubidium, or both, from ore.[0014] Fig. 2 is a floW diagram shoWing a further process of the present inVention for recoVering cesium, rubidium, or both.

DETAILED DESCRIPTION OF THE PRESENT | \l VENTION[0015] The present inVention relates to methods for recoVering at least cesium, rubidium, or both from ore or other material containing cesium and/ or rubidium. The present inVention also relates to cesium oxide or rubidium oxide obtained from these methods. id="p-16"

[0016] ln more detail, the cesium and/or rubidium can be of any form in the ore or othermaterial containing the cesium and/ or rubidium. For instance, the cesium can be present in anyore or other material as a cesium oxide. The rubidium can be present in any ore or othermaterial as rubidium oxide. Preferably, the ore includes cesium, such as pollucite (a cesiumaluminosilicate ore) With the preferred forrnula of CsAlSigOó. In many cases, the cesiumaluminosilicates also include rubidium. The ore can be a high-assay ore or a loW-assay ore. AloW-assay ore, also considered a secondary ore, can comprise 25 Wt% CsgO or less based on theoVerall Weight of the ore. id="p-17"

[0017] The ore (overall) can be or include 20 Wt% CsgO or less, 15 Wt% CsgO or less, 10Wt% CsgO or less, from 1 Wt% to 15 Wt% CsgO, from 1 Wt% to 10 Wt% CsgO, from 0.25 Wt%to 5 Wt% CsgO, less than 1 Wt% CsgO or about 0.1 Wt% CsgO or more or other low amounts ofcesium containing ore, or other amounts Within or outside of any one of these ranges based onthe total Wt% of the ore. The RbgO can be present in these same amounts alone or With theCsgO. id="p-18"

[0018] The ore (overall) can be or include 20 Wt% CsgO or more, 25 Wt% CsgO or more, 35Wt% CsgO or mores, from 20 Wt% to 35 Wt% CsgO, from 21 Wt% to 35 Wt% CsgO, from 25Wt% to 35 Wt% CsgO or more or other higher amounts of cesium containing ore, or otheramounts Within or outside of any one of these ranges based on the total Wt% of the ore. TheRbgO can be present in these same amounts alone or With the CsgO. id="p-19"

[0019] The ore can include, comprise, consist essentially of, or consist of pollucite,nanpingite, camallite, rhodozite, pezzottaite, rubicline, borate ramanite, beryls, Voloshonite, cesstibtantite, aVogadrite, margaritasite, kupletskite, naliVkinite, petalite, spodumene, lepidolite, biotite, mica, muscovite, feldspar, microcline, Li-muscovite, lithiophilite, amblygonite, illite,cookeite, albite, analcime, squi, amphiboles, lithian mica, amphibolite, lithiophospahe, apatiteand/ or londonite, or any combinations thereof. The ore can comprise, consist essentially of, orconsist of pollucite, an aluminosilicate mineral having the general forrnula(Cs>Na)[A1Si2O6]H2O. The ore can have at least 1 Wt% pollucite based on the Weight of theore, or from 1 to 5 Wt% pollucite based on the Weight of the ore, or at least 3 Wt% pollucitebased on the Weight of the ore. Other amounts are from 1 Wt% to 40 Wt% or from 1 Wt% to 35Wt%, or from 1 Wt% to 30 Wt%, or from 1 Wt% to 25 Wt% pollucite based on the Weight of theore. id="p-20"

[0020] The ore or other material containing at least cesium and/or rubidium can be in anyshape or size. Preferably, the ore or other material is in the form of particulates, poWder, or aplurality of particles. The ore or other material can be of a size of -200 mesh or smaller. Forinstance, at least 50% by Weight (or at least 60 Wt%, at least 70 Wt%, at least 80 Wt%, at least90 Wt%, at least 95 Wt%, from 50 Wt% to 100 Wt %) of the ore or other material can be presentas a powder or particulates having a mesh of -200 mesh. id="p-21"

[0021] The ore or other material can be present as particulates or poWder and have anaverage particle size of from about 1 mm to about 15 mm. For instance, the average particlesize can be from about 2 mm to about 12 mm. id="p-22"

[0022] If the ore or other material containing at least cesium and/or rubidium is recoveredas large pieces, such as over 15 mm in size, this ore or other material can be reduced toparticulates (for instance, to the sizes mentioned above) by crushing, milling, or other techniques. id="p-23"

[0023] With regard to the crusher, any crusher can be used that can reduce large rocks intosmaller rocks or individual pieces. Examples of crushers that can be used include, but are notlimited to, a jaW crusher, a gyratory crusher, a cone crusher, an impact crusher, such as ahorizontal shaft impactor, hammer mill, or Vertical shaft impactor. Other examples of crushersthat can be used include compound crushers and mineral sizers. As an option, a rock breakercan be used before crushing to reduce oVersized material too large for a crusher. Also, morethan one crusher can be used and/or more than one type of crusher can be used in order toobtain desirable sizes and processing speeds. id="p-24"

[0024] In an optional crushing step, preferably, the ore can be crushed to obtain crushed orethat is or includes powder or particles or particulates, Where at least 50% by Weight (e.g., orleast 60% or at least 70% or at least 80%, or at least 90%, or at least 95% or 100% by Weight)of the crushed ore has a size capable of passing through a mesh/screen of 200 mesh, or passingthrough a mesh/screen of 175 mesh, or passing through a mesh/screen of 150 mesh, or passingthrough a mesh/screen of 125 mesh, or passing through a mesh/screen of -200 mesh, but notpassing through +100 mesh (all U.S. mesh sizes). id="p-25"

[0025] In lieu of ore, examples of "other material" that contain at least cesium and/orrubidium that can be subjected to the methods of the present inVention include, but are notlimited to, tailings, and recycled material. id="p-26"

[0026] Regarding the at least one reactant that is heated With the ore or other materialcontaining cesium and/or rubidium, as indicated, this reactant can be one or more reactants.The reactant can be an oxide of a metal, or a carbonate of a metal, or a hydroxide of a metal, ora hydrate of a metal. The reactant is capable of displacing cesium oxide, rubidium oxide, or both from the ore or other material. Examples of the reactant include, but are not limited to, lime, hydrated lime, lime in solution, or calcium carbonate or any combination thereof Thereactant can be an oxide and/or hydrate and/or hydroxide and/or carbonate of calcium. Thereactant can be an oxide of strontium, an oxide of barium, an oxide of lithium, or anycombination thereof The reactant can be an oxide and/or hydrate and/or hydroxide and/orcarbonate of strontium, and/or can be an oxide and/or hydrate and/or hydroxide and/ orcarbonate of barium, and/or can be an oxide and/ or hydrate and/or hydroxide and/or carbonateof lithium. The reactant is not magnesium oxide. id="p-27"

[0027] The reactants can be present as a powder or particulates or particles or in otherforms. The reactant can be present as particulates or particles haVing a size of -200 mesh orsmaller. For instance, at least 50% by Weight (e.g., or at least 60%, or at 70%, or at least 80%,or at least 90%, or at least 95%, or at least l00% by Weight) of the reactant can haVe a size of -200 mesh. The reactant can be present as particulates haVing an aVerage particle size of fromabout l mm to about l5 mm, or from about 2 mm to about 12 mm. id="p-28"

[0028] Since the at least one reactant and the ore or other material containing the cesiumand/or rubidium are heated together, it is adVantageous that the ore or other material and thereactant haVe similar or the same particle sizes. For instance, the ore or other material and thereactant can each haVe a particle size (e.g., aVerage particle size) that is Within 50% of eachother or Within 25% of each other, or Within l0% of each other, or Within 5% of each other.[0029] For the heating of the reactant With the ore or other material containing the cesiumand/or rubidium, preferably the ore or other material is in intimate contact With the reactant.This can be achieVed by mixing the ore or other material With the reactant so that the reactant issubstantially uniforrnly distributed throughout the ore or other material. AltematiVely, the reactant can be non-uniforrnly distributed throughout the ore or other material. id="p-30"

[0030] The ore or other material and the at least one reactant can be used in various Weightratios. Preferably, the ore or other material and the at least one reactant have a Weight ratio ofore or other material : reactant of from about 15:85 to about 85:15 or, for instance, from about5:95 to about 95:5 or from about 40:60 to about 60:40. id="p-31"

[0031] The ore or other material and the reactant(s) can be mixed together prior to and/orduring the heating step. Any mixer can be used to accomplish the mixing of the two, such asan auger, mixer, blender, and the like. id="p-32"

[0032] Regarding the heating step, the heating is generally at a temperature of l,000° C orhigher. The temperature is a reference to the average temperature achieved by the ore or othermaterial. The temperature can be from about l,000° C to about 3,000° C or more, for instance,from about l,025° C to about l,750° C, or from about l,000° C to about 2,000° C, or fromabout l,025° C to about 3,000° C, or the temperature of the heating can be at a temperaturesufficient to volatize said cesium, rubidium, or both, that is present in the ore or other material,and this can be temperatures as stated here or above 3,000° C. id="p-33"

[0033] The heating can be accomplished in any apparatus or device typically used to heatminerals or ore. For instance, the heating can occur in a fiJmace (e.g., rotary fumace) or in anoven and the like. id="p-34"

[0034] The heating that is used in the present invention can be a single step heating processor staged heating or have multiple heating steps. The heating temperature can be achieved byramping up the temperature. For instance, the ramping of the temperature to the desiredtemperature to achieve liberation can be ramped up at least l° C per minute, at least 5° C per minute, at least l0° C per minute, or at least l5° C per minute, or more. id="p-35"

[0035] The heating can be done under pressure or under an inert atmosphere or in anoxygen-containing atmosphere, or under Vacuum or under a reductiVe environment (such as ina bed of carbon). id="p-36"

[0036] The heating can be for a period of 5 minutes or more, such as from about 5 minutesto 100 hours or more. Generally, the heating occurs until the available amount (or portionthereof) of cesium and/or rubidium is liberated from the ore or other material. Generally, theprocess can liberate at least 50% by Weight, at least 60% by Weight, at least 70% by Weight, atleast 80% by Weight, at least 90% by Weight, at least 95% by Weight, at least 98% by Weight, atleast 99% by Weight, or 100 Wt% of all aVailable cesium and/or rubidium present in the ore orother material. id="p-37"

[0037] During the heating process, the cesium and/or rubidium can be liberated, forinstance, in the form of a gas. The gas can be typically a cesium oxide and/or rubidium oxide.The cesium or rubidium or both, in the form of a gas, can be recoVered using Varioustechniques. For instance, the cesium and/or rubidium gas can be recoVered by scrubbing thegas With an aqueous solution or non-aqueous solution. The scrubbing of the gas can be doneWith Water or a salt solution or other solution. The recoVery of the cesium oxide or rubidiumoxide from the gas formed can be done by subjecting the gas to condensation temperatures, forinstance, spraying the gas With Water or other aqueous or non-aqueous solutions. id="p-38"

[0038] In the present inVention, the ore or other material, after the cesium and/or rubidiumare liberated, can be at least partially conVerted to calcium silicate, calcium aluminosilicate, orboth, When calcium is used as one of the reactants or as all of the reactant. id="p-39"

[0039] With the present inVention, the reaction efficiency of liberating cesium and/or rubidium Values from the ore or other material can be to a yield that is near complete extraction of the cesium oxide and/or rubidium oxide Values that are present in the ore or minerals orother materials. id="p-40"

[0040] Figure 1 sets forth a block diagram showing the Various steps of the methods of thepresent inVention including optional steps. The blocks or rectangles defined by dashed linesare optional steps. Referring to Figure 1, cesium bearing or ore material and/or rubidiumbearing or ore material is obtained (10) and optionally subjected to crushing or milling toreduce the size of the material (12) preferably to the particle sizes mentioned herein. Then, thematerial is introduced into an oVen or fiJrnace or other heating deVice (14) and a reactant (16) isalso introduced. As indicated, optionally the reactant and cesiun1/rubidium bearing materialcan be mixed prior to being introduced into the furnace, or can be mixed in the furnace.Further, the reactant and/ or cesium/bearing material can be introduced as batches, continuously,semi-continuously, and the like. Heat (18) is then introduced to the material and then cesiumand/or rubidium are liberated or displaced (20) such as cesium oxide and/or rubidium oxide. Asan option, the cesium oxide/rubidium can be liberated as a gas. The cesiun1/rubidium isseparated from the remaining ore/material (22). The remaining ore/material can be discarded,or retumed to the process (10 and/or 14) and/or for fiJrther processing. The liberated cesiumand/or rubidium (24) can then be converted to a liquid or subjected to condensation (28) andthen converted to cesium and/or rubidium salts or other products such as cesium forrnate,cesium hydroxide, cesium sulfate (32), and the like. Similar rubidium materials can be formedfrom rubidium When rubidium is the source material. id="p-41"

[0041] As an option, the ore/material can contain one or more salts. The one or more salts canbe naturally part of the ore/material (present in the starting ore/material). In the altematiVe, or in addition, the one or more salts can be added to the ore/material before and/or during the process of _10- the present inVention. The presence of one or more salts can perrnit a filrther reaction between theliberated cesium, rubidium, or both, and the salt, and this can forrn cesium salts and/or rubidiumsalts, such as but not limited to, cesium sulfate and/or rubidium sulfate. The adding of one or moresalts can be done prior to liberating of the cesium, rubidium or both from the ore or other material,and/or can be done during the liberating of the cesium, rubidium or both, and/or can be done afterthe liberating of the cesium, rubidium, or both. Preferably, the one or more salts are added beforeor during the liberating of the cesium, rubidium, or both. For instance, as the ore or other materialis heated With at least one reactant, the cesium and/or rubidium begin to decompose and eVentuallyare liberated. If one or more salts are present, the cesium and/or rubidium being release from theore or other material Will then react With the one or more salts. The cesium and/or rubidium, forinstance, can begin to decompose and be aVailable to react With any salt present at temperature ofabout l080° C to l090° C and higher. The reaction of the cesium and/or rubidium from the ore orother material generally reacts completely and quickly at temperatures of ll00° C or higher.Generally, if a salt(s) is present, it Will not react until the cesium and/or rubidium is decomposed orliberated from the ore or other material (e.g., When the cesium and/or rubidium is present as anoXide), or, otherwise rendered aVailable for further reaction With a salt. Generally, the reaction ofthe salt With cesium and/or rubidium is best conducted When the salt reaction is advanced to andbeyond temperatures that Where liquid phase diffusion is promoted, or enabled, and/or, up to suchtemperatures that promote the Vapor phase release of the comprised cesium and/or rubidiuminVentory (e.g., When the inVentory of cesium and/or rubidium is in the Vapor phase and the salt isin the Vapor phase). id="p-42"

[0042] As an option, beforehand, Water can be added to the ore or other material to leach any salt present in the ore or other material and as an option, the ore or other material can be _11- heated to concentrate the salt solution that Was formed from the leaching. For instance, the saltsolution can be concentrated to 30% to 50% by Weight in solution or more. id="p-43"

[0043] The salt that can be naturally present or added (to the ore or other material) can be,for instance, a sulfate salt, like a sulfate salt from Group I or Ila or Hb of the Periodic Table ofthe Elements, such as, for example, Li, Na, K, Rb, Cs, Mg, Ca, Sr, and/or Ba sulfates. The saltcan be a metal chloride salt (Li, Na, K, Rb, Cs, Mg, Ca, Sr, and/or Ba chloride). The salt usedcan be in any shape or size. Preferably, the salt is in a form that is capable of being in intimatecontact With the liberated cesium and/or rubidium. The salt can be in poWder form, Wherein atleast 80 Wt% of the poWder is about -200 mesh. To react the liberated cesium and/or rubidiumWith the salt, the two reactants can be mixed together. If added, the Weight ratio of salt toliberated cesium and/or rubidium is from 30% to about 85% by Weight liberated cesium orrubidium to 15% to about 70% by Weight salt. The mixture of salt and liberated cesium and/ orrubidium can be subjected to heat and up to temperature of from 500°C to 3,000°C or higher.This can be done by rotary kiln, or heating deVice or fiJmace. The heating time can be fromminutes to hours (e.g., 10 minutes to 10 hours or more). The cesium and/or rubidium saltformed from this second reaction can then be subjected to eVaporation techniques toconcentrate the cesium salt and/or rubidium salt (e.g., cesium sulfate) so as to precipitate outthe cesium salt and/or rubidium salt for easier recoVery. id="p-44"

[0044] Once the starting material is suitably decomposed, and the cesium and/or rubidiuminVentory (e.g., cesium salt, rubidium salt, or both) is reacted, formed, liberated, and released, ifthis occurs, the cesium and/or rubidium Values, and/or, the cesium salt and/or rubidium salt,Which can be in the Vapor phase, can be scrubbed or otherwise contacted With Water to form a salt solution, Which can then be concentrated as a salt solution by heating to remoVe or _12- evaporate some of the water. Or as an option, the cesium and/or rubidium values, liberated as avapor phase can be scrubbed or otherwise contacted with an acid (e.g., forrnic acid, acetic acid,etc...) to form a forrnate or acetate of the cesium and/or rubidium, and the like (e.g., cesiumforrnate, cesium acetate, rubidium forrnate, and/or rubidium acetate). Or, as an option, thecesium and/or rubidium values, liberated as a vapor phase can be scrubbed or otherwisecontacted with a base. id="p-45"

[0045] Figure 2 further sets forth a block diagram showing the various steps of the methodsof the present invention including optional steps involving the presence and/or addition of saltsto the process. The blocks or rectangles defined by dashed lines are optional steps. Referringto Figure 2, cesium bearing or ore material and/ or rubidium bearing or ore material is obtained(10) and optionally subjected to crushing or milling to reduce the size of the material (12)preferably to the particle sizes mentioned herein. Then, the material is introduced into an ovenor fiJmace or other heating device (14) and a reactant (16) is also introduced. One or more salts(36) can be introduced at any point or multiple points in the process as shown by the dashedarrows. One or more of these locations can be used to add salt. In the alternative, or in addition,salt(s) can be present as part of the ore or material (10). As indicated, optionally the reactantand cesiun1/rubidium bearing material can be mixed prior to being introduced into the fiJmace,or can be mixed in the fumace. Further, the reactant and/or cesiun1/bearing material can beintroduced as batches, continuously, semi-continuously, and the like. Heat (18) is thenintroduced to the material and then cesium and/or rubidium (e.g., cesium oxide and/or rubidiumoxide) are liberated or displaced (20). As an option, cesium oxide/rubidium can be liberated asa gas. Then, the cesium and/or rubidium (20) reacts with the salt(s) (38) to form cesium salt(s) and/or rubidium salt(s). The cesium salt(s) and/or rubidium salt(s) can be formed in the vapor _13- phase. The cesium salt and/or rubidium material is separated from the remaining ore/material(22). The remaining ore/material can be discarded, or retumed to the process (10 and/or 14)and/or for fiJrther processing. The cesium salt(s) and/or rubidium salt(s) can be recoVered (48).The cesium salt(s) and/or rubidium salt(s) can be scrubbed With Water or acid or an organicliquid (40) to obtain a solution (42) (e.g., a salt solution, a salt of the acid solution, an cesiumand/or rubidium organic solution). The solution can be subjected to eVaporation or othertechniques to concentrate the solution (44). Similar rubidium materials can be formed fromrubidium When rubidium is the source material. id="p-46"

[0046] As an option, the method can maintain a slight CO presence (e.g., l Wt% or less,such as 500 ppm or less in the solution, based on Wt of solution), Which can be adVantageous tofacilitate the recoVery of the cesium and/or rubidium. id="p-47"

[0047] The type of reactions that can be achieved With Various cesium-containing mineralsare provided below. HoWeVer, it is to be appreciated that While Pollucite is the mineralportrayed in the exemplary reaction shoWn beloW, other cesium-bearing minerals or ores can beused. Further, While calcium oxide is used as the preferred reactant, again, it is to be appreciated that other reactants can be used.

Reaction #1 (Larnitep CsgO AlgOg 4SiO2 + 8 CaO *b >1l5°°C caz A12 sio7 + 3 caz sio., + cszo 4*Llghtly Gehlenite LarniteSintered _14- Reaction #2 (Rankinite): CsgO AlgOg 4SiO2 + 61/2 CaO e :UÉEÉC caz A12 sio7+ 11/2 (Jag S12 o7+cs2o i.lg y Gehlenite RankiniteSintered Reaction #3 (W ollastonite): CsgO AlgOg 4SiO2 + 5 CaO ï> :UC caz A12 S107 + 3 ca S103 + C520 i.lg y Gehlenite WollastoniteSintered id="p-48"

[0048] As an option, the recovered CsgO can then be processed for a variety of uses. Forinstance, the CsgO can be used to form cesium compounds, such as cesium formate. Forinstance, the CsgO can be recovered and subjected to further recovery processes by reacting theCsgO With at least one salt, Where the salt is capable of recovering at least one metallic element,such as cesium, to form a reaction product that includes at least one metallic element. Forinstance, the salt can be a sulfate salt. Details of this further processing step can be found inU.S. Patent No. 7,323,l50, incorporated in its entirety by reference herein. By using thisprocess, the cesium can be converted to a precursor salt, such as cesium sulfate, from Whichother cesium salts are produced. Other methodology similarly can produce altemative cesiumsalts from precursors like cesium hydroxide and cesium carbonate. As described, for instance,in U.S. Patent No. 7,759,273, the cesium can be formed into a cesium formate Whichsubsequently can then be converted to a different cesium metal salt. Another process to formcesium salts is described in U.S. Patent No. 6,652,820, Which is incorporated in its entirety byreference herein. This method involves forming a cesium salt by reacting cesium sulfate With lime to form cesium hydroxide Which can then be converted to a cesium salt, such as cesium _15- formate. As stated, the cesium compounds can be Very desirable as drilling fluids or otherfluids used for hydrocarbon recovery, such as completion fluids, packer fluids, and the like.[0049] The processes described in U.S. Patent No. 6,0l5,535 can also be used to forrndesirable cesium compounds, such as cesium formate. The Various forrnulations andcompositions described in the following patents can be used with the cesium or cesiumcompounds recoVered by the processes of the present inVention and each of these patents areincorporated in their entirety by reference herein: U.S. Patent No. 7,407,008; 7,273,832;7,21 1,550; 7,056,868; 6,8l8,595; 6,656,989; and 6,423,802.[0050] The present inVention includes the following aspects/embodiments/features in anyorder and/or in any combination:l. A method for recoVering at least cesium, rubidium, or both from an ore or other material,said method comprising: heating a) said ore or other material, and b) at least one reactant together, wherein said heating is at a temperature sufficient to liberate at least a portion of saidcesium, rubidium, or both from said ore or other material, and said reactant is an oxide of a metal, or a carbonate of a metal, hydroxide of a metal or ahydrate of a metal, that is capable of displacing cesium oxide, rubidium oxide, or both from saidore or other material.2. The method of any preceding or following embodiment/feature/aspect, wherein saidreactant is lime, hydrated lime, lime in solution or calcium carbonate or any combination thereof3. The method of any preceding or following embodiment/feature/aspect, wherein said reactant is an oxide or hydroxide or hydrate or carbonate of calcium. _16- 4. The method of any preceding or following embodiment/feature/aspect, wherein saidreactant is an oxide of strontium, an oxide of barium, an oxide of lithium, or any combinationthereof. 5. The method of any preceding or following embodiment/feature/aspect, wherein saidtemperature of said heating is l,000° C or higher. 6. The method of any preceding or following embodiment/feature/aspect, wherein saidtemperature of said heating is from about l,000° C to about 2,000° C. 7. The method of any preceding or following embodiment/feature/aspect, wherein saidtemperature of said heating is from about l,025° C to about l,750° C. 8. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material is present as particulates. 9. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material is present as particulates in a size of about -200 mesh or smaller. 10. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material is present as particulates haVing at least 50% by weight of -200 mesh. 11. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material is present as particulates and haVing an aVerage particle size of from about 1 mm toabout 15 mm. 12. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material is present as particulates and haVing an aVerage particle size of from about 2 mm toabout 12 mm. 13. The method of any preceding or following embodiment/feature/aspect, wherein said reactant is present as particulates. _17- 14. The method of any preceding or following embodiment/feature/aspect, wherein saidreactant is present as particulates and having a size of about -200 mesh or smaller. 15. The method of any preceding or following embodiment/feature/aspect, wherein saidreactant is present as particulates and haVing at least 50% by weight of -200 mesh. 16. The method of any preceding or following embodiment/feature/aspect, wherein saidreactant is present as particulates and haVing an aVerage particle size of from about 1 mm to about15 mm. 17. The method of any preceding or following embodiment/feature/aspect, wherein saidreactant is present as particulates and haVing an aVerage particle size of from about 2 mm to about12 mm. 18. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material and said reactant or both are in particulate form and each haVe an aVerage particlesize that is within 50% of each other. 19. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material and said reactant or both are in particulate form and each haVe an aVerage particlesize that is within 25% of each other. 20. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material and said reactant or both are in particulate form and each haVe an aVerage particlesize that is within 10% of each other. 21. The method of any preceding or following embodiment/feature/aspect, wherein said ore ispresent and subjected to said heating. 22. The method of any preceding or following embodiment/feature/aspect, wherein said ore is present and is cesium-bearing ore. _18- 23. The method of any preceding or following embodiment/feature/aspect, wherein said ore ispresent and is silicate-based ore. 24. The method of any preceding or following embodiment/feature/aspect, wherein said ore ispresent and is aluminosilicate-based ore. 25. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material is in intimate contact with said at least one reactant. 26. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material and said at least one reactant haVe a weight ratio of said ore or other material to saidreactant of from about l5:85 to about 85:15. 27. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material and said at least one reactant haVe a weight ratio of said ore or other material to saidreactant of from about 5:95 to about 95:5. 28. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material and said at least one reactant haVe a weight ratio of said ore or other material to saidreactant of from about 40:60 to about 60:40. 29. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material and said at least one reactant are mixed together prior to or during said heating. 30. The method of any preceding or following embodiment/feature/aspect, fiarther comprisingrecoVering said cesium or rubidium or both. 31. The method of any preceding or following embodiment/feature/aspect, fiarther comprising recoVering cesium or rubidium or both in the form of a gas. _19- 32. The method of any preceding or following embodiment/feature/aspect, fiarther comprisingrecovering said cesium or rubidium or both in the form of a gas and converting said gas to a liquidsolution containing cesium or rubidium or both. 33. The method of any preceding or following embodiment/feature/aspect, fiarther comprisingrecovering cesium or rubidium or both in the forrn of a gas, wherein said cesium or rubidium orboth are in the forrn of an oxide. 34. The method of any preceding or following embodiment/feature/aspect, fiarther comprisingscrubbing said gas with an aqueous solution or non-aqueous solution. 35. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material, after said liberating, is at least partially conVerted to calcium silicate, calciumaluminosilicate, or both. 36. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material is present and comprises pollucite. 37. The method of any preceding or following embodiment/feature/aspect, wherein saidheating is under pressure. 38. The method of any preceding or following embodiment/feature/aspect, wherein saidheating is under an inert atmosphere. 39. The method of any preceding or following embodiment/feature/aspect, wherein saidheating is in an oxygen-containing atmosphere. 40. The method of any preceding or following embodiment/feature/aspect, wherein saidheating is under Vacuum. 4l. The method of any preceding or following embodiment/feature/aspect, wherein said heating is under a reductiVe environment. _20- 42. The method of any preceding or following embodiment/feature/aspect, wherein saidheating is for a period of 5 minutes or more. 43. The method of any preceding or following embodiment/feature/aspect, wherein saidhearing is for a period of from about 5 minutes to 100 hours. 44. Cesium oxide or rubidium oxide obtained from the method of any preceding or followingembodiment/feature/aspect. 45. The method of any preceding or following embodiment/feature/aspect, wherein saidtemperature of said heating is from about l,025° C to about 3,000° C. 46. The method of any preceding or following embodiment/feature/aspect, wherein saidtemperature of said heating is at a temperature sufficient to Volatize said cesium, rubidium, orboth. 47. The method of any preceding or following embodiment/feature/aspect, wherein said ore orother material fiJrther comprises at least one salt, and wherein said at least one salt reacts with saidat least a portion of said cesium, rubidium, or both to form a cesium salt or a rubidium salt or both.48. The method of any preceding or following embodiment/feature/aspect, wherein at leastone salt comprises a chloride. 49. The method of any preceding or following embodiment/feature/aspect, wherein at leastone salt comprises a sulfate. 50. The method of any preceding or following embodiment/feature/aspect, wherein saidmethod further comprises adding at least one salt prior to or during said heating. 5l. The method of any preceding or following embodiment/feature/aspect, wherein said atleast one salt reacts with said at least a portion of said cesium, rubidium, or both to form a cesium salt or a rubidium salt or both. _21- 52. The method of any preceding or following embodiment/feature/aspect, wherein saidcesium salt or rubidium salt comprises cesium sulfate, cesium chloride, rubidium sulfate, orrubidium chloride. 53. The method of any preceding or following embodiment/feature/aspect, wherein saidcesium salt or rubidium salt comprises cesium sulfate, cesium chloride, rubidium sulfate, orrubidium chloride. 54. The method of any preceding or following embodiment/feature/aspect, wherein methodfiJrther comprises scrubbing said cesium salt or rubidium salt or both in Vapor phase with water oran acid or a base. 55. The method of any preceding or following embodiment/feature/aspect, wherein methodfiJrther comprises scrubbing said cesium salt or rubidium salt or both in Vapor phase with water oran acid or a base. id="p-51"

[0051] The present inVention can include any combination of these Various features orembodiments above and/or below as set forth in sentences and/or paragraphs. Any combinationof disclosed features herein is considered part of the present inVention and no limitation isintended with respect to combinable features. id="p-52"

[0052] Applicants specifically incorporate the entire contents of all cited references in thisdisclosure. Further, when an amount, concentration, or other Value or parameter is given as either arange, preferred range, or a list of upper preferable Values and lower preferable Values, this is to beunderstood as specifically disclosing all ranges formed from any pair of any upper range limit orpreferred Value and any lower range limit or preferred Value, regardless of whether ranges areseparately disclosed. Where a range of numerical Values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the _22- range. It is not intended that the scope of the inVention be limited to the specific values recitedWhen defining a range. id="p-53"

[0053] Other embodiments of the present inVention Will be apparent to those skilled in theart from consideration of the present specif1cation and practice of the present inVentiondisclosed herein. It is intended that the present specification and examples be considered asexemplary only With a true scope and spirit of the inVention being indicated by the following claims and equiValents thereof. _23-

Claims (4)

1. WHAT IS CLAIMED IS:l. A method for recovering at least cesium, rubidiurn, or both from an ore or other material,said method comprising: heating a) said ore or other material, and b) at least one reactant together, Wherein said heating is at a temperature sufficient to liberate at least a portion of saidcesium, rubidium, or both from said ore or other material, and said reactant is an oxide of a metal, or a carbonate of a metal, hydroxide of a metal or ahydrate of a metal, that is capable of displacing cesium oxide, rubidium oxide, or both from said ore or other material.

2. The method of claim l, Wherein said reactant is lime, hydrated lime, lime in solution or calcium carbonate or any combination thereof.

3. The method of claim l, Wherein said reactant is an oxide or hydroxide or hydrate or carbonate of calcium: 41 ------------- -flïlae--metlæod-of-eflaiffn--lç--W-lfaere-inggr said reactant is an oxide of strontium, an oxide of barium, an oxide of lithiurn, or any combination thereof -1-1-1: ---------- -fí-ïhfe--næethod-o-íï-e-laina--1--;-ævherei-n-saieï-or-e--e-r-otšrer-niate-riai»is-present-as-ïæ-artieæii-ates-haäli-fi-g at--1east--â-š-fiéy-by-æveight-ofwëí-šíè-ineshf l--1-šå. The method of c1aim 1, Wherein said ore or other material is present as particu1ates and having an average partic1e size of from about 1 mm to about 15 mm. 1%. ---------- -fí-ïhef-inetšrod;-o-f-ei-ai-næ-4;--W-šierein--sai-á--ore--e-r-other--ni-ate-ráai»is»present--as-ïæ-artieæii-ates--ané having-an-éwerage-fa-:aeiftiefle-size--of-from-aboat--šš-mni--to-abeiæt--š--šf-næ-rnf The method of c1aim 1, Wherein said ore or other materia1 and said reactant or both are in particulate form and each haVe an average partic1e size that is Within 50% of each other. fï til. ---------- -fl-ïhef-nte-thod--of-eflaim--1-;--W-herei-n--sai-á-ere-e-r-other-ni-ateria1--anel-said-reastasit--tafr-åäeth--are--i-rr parâieu-late-ärm--a:id-eaeh-have»af1--average--partis-le-size-that-is-Witlrin---1-(-}9~4y-o§eae-l=a--ot-l=aerf 2--1-1 ---------- -ïlïhe-metired-of-elaim--1-;--where-in-said-ore»is--pfiesent-and-sæælagje-eted-to-said-hefitingf Sååå. The method of claim 1, Wherein said ore is present and is cesium-bearing ore: t silicate-based ore: . , or aluminosilicate-based ore. The method of claim 1, Wherein said ore or other material and said at least one reactanthaVe a Weight ratio of said ore or other material to said reactant of from about 15:85 to about 85:15. 34--, ---------- -fi-ïhef-method--e»f-e-lai-rn-»l-;--furthe-r-eonægarising--reeoæßering--eesium-of-iubidi-unæ-or--both--in--tlie forinoJf-a-gï" s:- åšå. The method of claim 1, further comprising recoVering said cesium or rubidium or both inthe form of a gas and conVerting said gas to a liquid solution containing cesium or rubidium or both. å; -. ---------- -fi-ïhef-method--e»f-eflai-rn-»l-;--further-eonægarising--reeofiæering--eesium-of-iubidi-unæ-or--botli--in--tlie foflra-ofa-g" s;--Wherein-said-eesiarn--e-r-rubidiæim-or-both-are-in-tlie--forin-oâafi--oxidef å-íšå. The method of claim l, Wherein said ore or other material, after said liberating, is at least partially conVerted to calcium silicate, calcium aluminosilicate, or both. The method of claim l, Wherein said ore or other material is present and comprises pollucite. f-Fhe-met-hod--e-fï-eflai-rn--l-ç-Wiierein»saié-heating--is-æineïer-ælaeuurn;f-ï-l-f --------- --ïïhe-nietherï»of-eflaim»l-;-Wherein--said-heating-is-under-a-re-duetiwe-enæliienmeaët; 4%-, ---------- -fl-ïhe--metlred-effel-ai-n1-»l-;--Whereén-said-hearirig-is-fefr-a-perie-d-offrom-ab:afut-ä-rnisiutfes-taaf--l--Q-G hours:- 4

4. --------- --Gesi-um--oëeiëe-or--Hibirliam--oxiée-obtained-from-the--inethod-ofaray-one-oš-e-lainis--hfiï-š; 4511. The method of claim l, Wherein said temperature of said heating is from about l,025° C to about 3,000° C. 4912. The method of claim l, Wherein said ore or other material filrther comprises at least one salt, and Wherein said at least one salt reacts With said at least a portion of said cesium, rubidium, or both to form a cesium salt or a rubidium salt or both. The method of claim l, Wherein said method fiJrther comprises adding at least one salt prior to or during said heating. âQ-ulueí, The method of claim 4412, Wherein said cesium salt or rubidium salt comprises cesium sulfate, cesium chloride, rubidium sulfate, or rubidium chloride. -šf-figluj, The method of claim 4~¥_E__;2._, Wherein method further comprises scrubbing said cesium salt or rubidium salt or both in Vapor phase With Water or an acid or a base. -S-É -. ---------- -ïiïhe»naethoé-oå;hafim:-fšà;-Whereí-fl-methodå;rt-her--eoraæfari-ses-ser-ufbbhag-saié-efesiæa-rææ-saÉt-or aaåhié-íaaææ-sal-t-orhot-h--í-n--vapor-pfšæasea-wi-th-water-erari-»aeíé-or-a--basef 16. (Éesiurn oxide or rubídiurn oxide obtained front the :method of anv one of clairns LI S,